EP0975557A1 - A method of treating cement clinker - Google Patents
A method of treating cement clinkerInfo
- Publication number
- EP0975557A1 EP0975557A1 EP19980912852 EP98912852A EP0975557A1 EP 0975557 A1 EP0975557 A1 EP 0975557A1 EP 19980912852 EP19980912852 EP 19980912852 EP 98912852 A EP98912852 A EP 98912852A EP 0975557 A1 EP0975557 A1 EP 0975557A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- agent
- slurry
- mill
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000010440 gypsum Substances 0.000 claims abstract description 6
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 9
- 235000019738 Limestone Nutrition 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000011398 Portland cement Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a method of treating cement clinker and more specifically to a method of treating cement clinker in the process of grinding the same.
- the cement clinker to which the invention relates is preferably Portland cement clinker, although it is not restricted to Portland cement clinker, but can be applied with other cement clinkers.
- the resultant ground cement will have a reduced water requirement and also greater strength in comparison with standard Portland cement.
- One decisive drawback with this method is the difficulty in controlling the extent of the reaction between Portland clinker and water reduction agent, this reaction having a direct influence on the instability of the properties of the final cement.
- the same reduction in water requirement can also be achieved by adding a water reduction agent directly to concrete with water, in accordance with conventional methods. No appreciable increase in the chemical reactivity of Portland clinker can be achieved with these methods.
- the present invention relates to a method of treating cement clinker whilst grinding the clinker and adding different substances thereto, in order to enhance the strength properties of the cement produced.
- the present invention thus relates to a method of treating cement clinker, by grinding the clinker in a tubular mill whilst adding water and gypsum and possibly also a water reduction agent, wherein the method is characterized by injecting water that has a pH of approximately 9-13 into the mill during grinding of the clinkers.
- Cement clinker is normally processed by first heating the clinker or calcine in a kiln at a temperature of 900-1450°C, such as to form the compounds 3 CaO Si0 2 , 2 CaO Si0 2 , 3 CaO A1 2 0 3 and 4 CaO A1 2 0 3 Si0 2 . This treatment process results in normal Portland cement.
- the clinker is ground together with gypsum to particle sizes of between 10-20 micrometers, in a tubular mill that includes steel balls. Water is added during this grinding process.
- the present invention relates to this second stage.
- the water has a pH of about 9-13 and is injected into the mill during grinding of the clinkers.
- the water injected has been brought to this pH-value by means of electrolysis.
- OH " -ions are thus injected into the mill. These ions constitute highly reactive radicals that fasten to the surfaces of the non-hydrated cement particles, and facilitate formation of the complex qCaO'mSi0 2 "nH 2 0. This complex is formed on the surfaces of the cement particles.
- the particles are prehydrated, they are very reactive. Adsorption of OH " -radicals on the surfaces of the clinker particles results in said complex-building and activation by virtue of the formation of a film of hydrosilicates on the particles. This complex acts as a nucleant for subsequent reaction with water. In combination, this results in a significant improvement in the strength development of cement paste and a reduced porosity, as will be evident from the following examples.
- a microfill agent and/or a water-reduction agent is/are added during the grinding process.
- part of the microfill agent and/or the water- reduction agent are mixed with said water of high pH-value to form a slurry which is injected into the mill during the grinding process, while adding dry microfill agent and/or water-reduction agent during the grinding process .
- the water-reduction agent is slurried and that this slurry is brought to said pH-value by electrolysis, prior to injecting the slurry into the mill.
- the ratio between the dry substance/substances and the slurry will preferably lie in a range of between 95 weight. / 5 weight% to 85 weight. / 15 weight..
- the liquid phase of the slurry will preferably not exceed 50% of the weight of the slurry.
- microfill agent in the form of Si0 2 -containing substances such as blast furnace slag and limestone, are delivered to the tubular mill in a quantity of up to 80% of the combined weight of microfill agent, water-reduction agent and water delivered to the mill.
- water-reduction agent in the form of polymers such as lignosulfonate-based polymers that contain naphthalene or melamine or combinations thereof are delivered to the tubular mill in an amount of up to 5% of the combined weight of microfill agent, water- reduction agent and water delivered to the mill.
- the letter C in this composition is an abbreviation of CaO, A is an abbreviation of A1 2 0 3 and F is an abbreviation of Fe 2 0 3 .
- the tubular mill measured 1.5 in diameter and 3.5 m in length. Gypsum was charged together with the Portland cement clinker in an amount corresponding to 3% of the weight of the clinker, together with non-distilled water taken from the normal water supply ' system.
- This water had been subjected to electrolysis in a direct current field having an amperage of 1.75 A/dm 2 and a voltage of 380 V for two minutes, so as to obtain a pH- value of 11.2.
- the water was delivered to the tubular mill in a dispersed form.
- the cement produced had a specific surface area (Blaine) of 4800 cmVg.
- the cement thus obtained was mixed with water in a Hobart mixer for three minutes, to obtain a cement paste of standard consistency.
- the cement paste was poured into a cubic steel mould having sides 20 mm in height, and compacted on a vibration table.
- the cement paste sample was cured in water at 20°C and then subjected to compression tests.
- Example 1 A Portland cement clinker according to that described in Example 1 was ground in a traditional manner and a cement paste sample was produced in accordance with Example 1 above.
- a Portland cement clinker corresponding to the clinker defined in Example 1 was ground in accordance with Example 1 together with pre-ground limestone as a microfill agent, said limestone having a specific surface area (Blaine) of 3000 cmVg.
- the total weight of the pre-ground limestone corresponded to 15 weight% of the weight of the cement and was charged in two different states, namely 80% in a solid, dry state and 20% in a state slurried with 35% water.
- the liquid phase of the slurry comprised tap water that had been electrolysed with 3.5 A/dm 2 and 380 V over a period of two minutes, to obtain a pH of 11.5.
- the slurry was charged to the tubular mill in a dispersed state.- The slurry was charged to the mill together with clinker, gypsum and the dry microfill agent.
- the cement produced had a specific surface area (Blaine) of 4780 cm 2 /g.
- the procedure followed in this example was the same as that used in Example 1, but with the exception that in this case a liquidizing agent was added to the system.
- the liquidizing agent was in the form of a 40%-solution of a melamine type superplasticizing agent, namely Flyt 92® produced by Cementa AB, Sweden.
- the liquidizing agent was added in an amount corresponding to one weight% of the total mill charge.
- the liquidizing agent was added to the liquid phase of the slurry prior to subjecting the same to electrolysis.
- Example 5 The procedure followed in this example was the same as that used in Example 2, i.e. traditional grinding, but with the exception that the liquidizing agent according to Example 5 was added with water in a conventional manner in the same quantity as that in Example 5, during casting of the cement paste.
- Example 2 The procedure followed in this example was the same as that followed in Example 1.
- the cement paste obtained was then treated in accordance with the method described in International Patent Application W094/25411 (PCT/SE94/00389) , wherein the cement paste was treated in a vibratory mill having a vibration circle of 10 mm in diameter and operating at a .frequency of 110 r.p. ., over a period of thirty minutes.
- the weight ratio of grinding media to mixture was 9:1.
- the "required water quantity” column in the Table denotes the amount of water that is required to produce a cement paste of standard consistency in percentage of the cement weight.
- the cement paste produced in accordance with the inventive method has a greater mechanical strength and a reduced priority.
- the water requirement is roughly the same.
- the present invention provides a Portland cement of considerably higher chemical reactivity than that of normal Portland cement, which is reflected in the fact that the cement paste cures more quickly at a given strength and obtains a significantly higher final strength.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Disintegrating Or Milling (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Crushing And Grinding (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9701129A SE510766C2 (en) | 1997-03-26 | 1997-03-26 | Procedure for treating cement clinker |
SE9701129 | 1997-03-26 | ||
PCT/SE1998/000529 WO1998042629A1 (en) | 1997-03-26 | 1998-03-23 | A method of treating cement clinker |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0975557A1 true EP0975557A1 (en) | 2000-02-02 |
EP0975557B1 EP0975557B1 (en) | 2001-07-25 |
Family
ID=20406338
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98912852A Expired - Lifetime EP0975557B1 (en) | 1997-03-26 | 1998-03-23 | A method of treating cement clinker |
Country Status (29)
Country | Link |
---|---|
US (1) | US6241816B1 (en) |
EP (1) | EP0975557B1 (en) |
JP (1) | JP2001518876A (en) |
KR (1) | KR100544450B1 (en) |
CN (1) | CN1166579C (en) |
AT (1) | ATE203500T1 (en) |
AU (1) | AU725470B2 (en) |
BR (1) | BR9808419A (en) |
CA (1) | CA2284288C (en) |
CZ (1) | CZ294934B6 (en) |
DE (1) | DE69801221T2 (en) |
DK (1) | DK0975557T3 (en) |
EE (1) | EE04186B1 (en) |
ES (1) | ES2162433T3 (en) |
GR (1) | GR3037016T3 (en) |
HK (1) | HK1026194A1 (en) |
HU (1) | HU221747B1 (en) |
ID (1) | ID24061A (en) |
IL (1) | IL131898A (en) |
NO (1) | NO324615B1 (en) |
NZ (1) | NZ337943A (en) |
PL (1) | PL192077B1 (en) |
PT (1) | PT975557E (en) |
RU (1) | RU2194676C2 (en) |
SE (1) | SE510766C2 (en) |
SK (1) | SK282715B6 (en) |
TR (1) | TR199902320T2 (en) |
UA (1) | UA53698C2 (en) |
WO (1) | WO1998042629A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000281419A (en) * | 1999-03-29 | 2000-10-10 | Sumitomo Osaka Cement Co Ltd | Production of mixed cement |
DE10003283A1 (en) * | 2000-01-26 | 2001-08-02 | Krupp Polysius Ag | Process and plant for the heat treatment of fine-grained material |
AU2001286233A1 (en) * | 2000-09-13 | 2002-03-26 | Denki Kagaku Kogyo Kabushiki Kaisha | Cement composition |
US6740155B1 (en) | 2001-08-24 | 2004-05-25 | Isg Resources, Inc. | Method of delaying the set time of cement and the compositions produced therefrom |
US6827776B1 (en) | 2001-08-24 | 2004-12-07 | Isg Resources, Inc. | Method for accelerating setting of cement and the compositions produced therefrom |
SE524154C2 (en) * | 2002-11-07 | 2004-07-06 | Procedo Entpr Ets | Process for producing mixed cement with reducing carbon dioxide emissions |
SE527086C2 (en) * | 2004-05-13 | 2005-12-20 | Procedo Entpr Etablissement | Process system for producing a composite of cementite material with reduced carbon dioxide emissions |
CN102219404A (en) * | 2011-03-29 | 2011-10-19 | 许兴康 | Preparation method of ultrafine slag slurry |
CN102241486A (en) * | 2011-03-29 | 2011-11-16 | 许兴康 | Cement mortar fast grinding method |
JP6097266B2 (en) * | 2014-10-06 | 2017-03-15 | 宇部興産株式会社 | Method for producing water-soluble hexavalent chromium-reducing cement composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3689294A (en) * | 1971-06-14 | 1972-09-05 | Stephen Braunauer | Portland cement compositions and method |
SU876583A1 (en) * | 1977-10-03 | 1981-10-30 | Московский ордена Ленина и ордена Трудового Красного Знамени химико-технологический институт им. Д.И.Менделеева | Method of intensifying grind of portlandcement clinker |
BE891434A (en) * | 1981-12-10 | 1982-03-31 | Cbr Cementbedrijven Nv | CEMENT MANUFACTURING PROCESS AND CEMENT OBTAINED BY THIS PROCESS |
CS274849B2 (en) * | 1989-03-30 | 1991-11-12 | Ustav Chemie Skelnych A Kerami | Method of portland clinker grinding for plasterless portland cements production |
SU1675255A1 (en) * | 1989-04-18 | 1991-09-07 | Белгородский технологический институт строительных материалов им.И.А.Гришманова | Method of cement grinding |
ES2050604B1 (en) | 1992-06-25 | 1994-12-16 | Low Water Binder Sa | MANUFACTURING PROCEDURE FOR A BINDER WITH LOW DEMAND FOR WATER. |
-
1997
- 1997-03-26 SE SE9701129A patent/SE510766C2/en not_active IP Right Cessation
-
1998
- 1998-03-23 TR TR1999/02320T patent/TR199902320T2/en unknown
- 1998-03-23 CZ CZ19993367A patent/CZ294934B6/en not_active IP Right Cessation
- 1998-03-23 ES ES98912852T patent/ES2162433T3/en not_active Expired - Lifetime
- 1998-03-23 ID ID991081D patent/ID24061A/en unknown
- 1998-03-23 RU RU99122702A patent/RU2194676C2/en not_active IP Right Cessation
- 1998-03-23 HU HU0000711A patent/HU221747B1/en not_active IP Right Cessation
- 1998-03-23 AT AT98912852T patent/ATE203500T1/en active
- 1998-03-23 KR KR1019997008485A patent/KR100544450B1/en not_active IP Right Cessation
- 1998-03-23 DE DE1998601221 patent/DE69801221T2/en not_active Expired - Lifetime
- 1998-03-23 NZ NZ33794398A patent/NZ337943A/en not_active IP Right Cessation
- 1998-03-23 UA UA99105773A patent/UA53698C2/en unknown
- 1998-03-23 WO PCT/SE1998/000529 patent/WO1998042629A1/en active IP Right Grant
- 1998-03-23 CA CA 2284288 patent/CA2284288C/en not_active Expired - Fee Related
- 1998-03-23 BR BR9808419A patent/BR9808419A/en not_active IP Right Cessation
- 1998-03-23 EP EP98912852A patent/EP0975557B1/en not_active Expired - Lifetime
- 1998-03-23 PL PL335874A patent/PL192077B1/en not_active IP Right Cessation
- 1998-03-23 PT PT98912852T patent/PT975557E/en unknown
- 1998-03-23 JP JP54556298A patent/JP2001518876A/en active Pending
- 1998-03-23 IL IL13189898A patent/IL131898A/en not_active IP Right Cessation
- 1998-03-23 EE EEP199900433A patent/EE04186B1/en not_active IP Right Cessation
- 1998-03-23 AU AU67540/98A patent/AU725470B2/en not_active Ceased
- 1998-03-23 US US09/381,481 patent/US6241816B1/en not_active Expired - Fee Related
- 1998-03-23 SK SK1279-99A patent/SK282715B6/en not_active IP Right Cessation
- 1998-03-23 DK DK98912852T patent/DK0975557T3/en active
- 1998-03-23 CN CNB988036800A patent/CN1166579C/en not_active Expired - Fee Related
-
1999
- 1999-09-23 NO NO19994629A patent/NO324615B1/en not_active IP Right Cessation
-
2000
- 2000-09-04 HK HK00105536A patent/HK1026194A1/en not_active IP Right Cessation
-
2001
- 2001-10-25 GR GR20010401886T patent/GR3037016T3/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9842629A1 * |
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